Optical absorption studies for TeO2-P2O5 and Bi2O3-TeO2-P2O5 glasses

A range of TeO₂-P₂O₅ and Bi₂O₃-TeO₂-P₂O₅ glass systems were prepared. The optical absorption spectra were measured in the spectral range 300–800 nm and it was found that the fundamental absorption of these glasses is dependent on the glass composition. The optical energy gap of binary glasses increases with increasing TeO₂ content while the addition of Bi₂O₃ to TeO₂-P₂O₅ decreases the optical energy gap. The absorption edges of these glasses arise from direct forbidden transitions and occur at photon energies in the range of 2.17 to 2.97 eV for TeO₂-P₂O₅ glasses and 2.63 to 2.32 eV for Bi₂O₃-TeO₂-P₂O₅ glasses depending on their composition.     

Infrared spectra of the vitreous system Co3O4-P2O5 and their interpretation

The infrared absorption spectra of the vitreous Co₃O₄-P₂O₅ system have been measured in the frequency region 4000 to 200 cm^–1. Absorption bands and mode attributions have been fully discussed. Absorption frequencies and intensities are found to be strongly and systematically dependent on glass composition. On this basis it is found that this glass system can be divided into three distinct compositional regions. Similar three region behaviour is reported for the compositional dependence of density and molar volume of mixing of Co₃O₄-P₂O₅ glass. Quantitative justification for the band attributions has been attempted.On leave from the Physics Department, Faculty of Science, Monofia University, Shebeen El-Kome, Egypt.     

A.c. conductivity for amorphous TeO2-P2O5 glass system

The a.c. conductivity for the TeO₂-P₂O₅ glassy system was measured in the temperature range 300–573 K and in the frequency range 100 Hz to 10 kHz. The a.c. conductivity () increased with frequency according to the relation ()^s. The frequency exponent s was found to decrease with increasing temperature. The composition dependence of the conductivity was also investigated. The density of states was also calculated using the Elliott model. The a.c. conductivity increased over the studied temperature range. The obtained experimental data have been analysed with reference to various theoretical models. The analysis shows that the correlated barrier hopping (CBH) model is the most appropriate mechanism for conduction in the TeO₂-P₂O₅ glass system.     

Mechanochemical synthesis of hydroxyapatite from Ca(OH)2-P2O5 and CaO-Ca(OH)2-P2O5 mixtures

Dry grinding of Ca(OH)₂-P₂O₅ and CaO-Ca(OH)₂-P₂O₅ mixtures was conducted by a planetary ball mill to investigate the mechanochemical solid-phase reaction for the synthesis of hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂, HAp). HAp was synthesized by grinding of the two sets of mixtures. The formation of HAp from the Ca(OH)₂-P₂O₅ mixture was more advantageous than that from the CaO-Ca(OH)₂-P₂O₅ one. This synthesis reaction from the former mixture was almost completed within 30 min of grinding. The presence and amount of H₂O contained in the starting mixtures played a key role to promote the formation of HAp. Especially, in the former mixture, the prolonged grinding assisted the solid-phase reaction of the intermediate DCPD and Ca(OH)₂ to produce HAp more effectively.     

Infrared spectra and composition dependence investigations of the vitreous V2O5/P2O5 system

A series of glasses in the V₂O₅-P₂O₅ system was prepared and their compositions analysed. The glass densities and molar volumes were determined. The results obtained revealed three compositional regions. In addition, the infrared absorption spectra of these glasses were measured at room temperature in the frequency range 1600–200 cm^–1. The compositional dependence of the bands present, attributed to a given band and mode of vibration, was investigated. However, the infrared data confirmed the results obtained from the density and molar volume measurements.     

Infra-red spectra of crystalline phases and related glasses in the TeO2-V2O5-Me2O system

The crystal line phases Me₂O·V₂O₅·2TeO₂ (Me=Li, Na, K, Cs, Ag) and their glasses are studied with the aid of infra-red spectroscopy. The radial distribution function (RDF) curves of two glasses, Na₂O·V₂O₅·2TeO₂ and Cs₂O·V₂O₅·2TeO₂, are obtained by an X-ray diffraction study. An attempt is made to identify the main bands in the infra-red spectra of the crystalline compounds and the glasses. The absorption bands in the 970 to 880 cm^–1 range are assigned to the stretching modes of the VO₂ isolated groups. A trend is observed towards a shift of the high-frequency band by the replacement of an alkaline ion with another in the order Ag⁺, Cu⁺, Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, which is explained by their different polarizing ability. With the aid of X-ray diffraction studies it is shown that the basic structure units in the glasses studied are the VO₄ and TeO₄ groups.     

Low temperature synthesis of glassy solids of the system Al2O3-P2O5-SiO2

Glassy solids of the system Al₂O₃-P₂O₅-SiO₂, which have not been obtainable because of the devitrification of glass during the cooling process after melting, were obtained by the gel method. After the gels of the system Al₂O₃-P₂O₅-SiO₂ were prepared from AlCl₃·6H₂O, H₃PO₄ and Si(OC₂H₅)₄, they were heat treated up to 800° C to obtain glassy solids. In SiO₂ concentrations ranging from 75 to 82 mol % in batch compositions, non-porous transparent solids were obtained, while in SiO₂ concentrations above 87 mol %, porous transparent solids were obtained. Tridymite was precipitated because of the crystallization of glassy solids during heat treatment above 800° C. It depended upon the microstructure of the gels whether non-porous glassy solids were obtained or not. The thermal expansion coefficients of the glassy solids were greatly dependent upon the concentration of P₂O₅, ranging from 1.7×10⁻⁶ to 4.2×10⁻⁶ (1/° C).     

The structure of glasses in the TeO2-P2O5 system

The co-effects of two glass-formers in the TeO₂-P₂O₅ system are studied on the basis of neutron diffraction data. The curves for the radial distribution function (RDF) obtained show a high extent of destruction of the short-range order in the tellurite matrix, while the basic co-ordination PO₄ polyhedron remains unchanged. The co-ordination number (cn) of the Te atom changes from 4 to 3+1 and marked tendency towards elongation of the Te-O distances over 2.3 Å is observed. The considerably higher stability of the PO₄ polyhedra and their strong influence on the TeO₄ polyhedra is established. The observed smearing effect of the Te-Te, Te-second O and O-second O distances in the range of 3.8 to 3.9 Å in other tellurite glasses is also characteristic of this system. A structural interpretation of the liquid-liquid immiscibility on the short-range order level in the system is given. A critical composition with 26±5% of the second glass-former is established, above which concentration a stable immiscibility in the tellurite systems is observed. An attempt is made to construct two adequate structural models (microhomogeneous and microheterogeneous) for the short-range order in the glasses studied.     

Phase equilibria and immiscibility in the TeO2-P2O5 system

The phase equilibria and immiscibility of mutual glass formers up to 50 mol% P₂O₅ have been studied. Phase analysis indicates the formation of three new phases — incongruent melting Te₄P₂O₁₃, Te₂P₂O₉, and a supposed metacompound. Electron microscope investigations established stable and metastable phase separation. The immiscibility confines the tendency to glass formation up to 25.8 mol % P₂O₅. A reliable interpretation in relation to the morphology of liquid-liquid immiscibility and crystallization is considered.     

Synthesis and properties of thin SiO2-P2O5-CaO films

Thin SiO₂-P₂O₅-CaO films have been produced by a sol-gel process from film-forming solutions. The physicochemical processes underlying the formation of the films have been investigated, and their phase composition, structure, and bioactivity have been determined.     

Study of structures and properties of ZnO-Sb2O3-P2O5-Na2O glasses

The influence of ZnO substitution by 0–12 wt.% Na₂O on the properties of ZnO-Sb₂O₃-P₂O₅-Na₂O glasses has been investigated. The structure and properties of the glasses with the composition of (13.86-x)ZnO-57.93Sb₂O₃-28.21P₂O_5?x Na₂O (x = 0–12 wt.%) were characterized by infrared spectra (IR), X-ray diffraction and differential thermal analysis (DTA). The results of IR indicated an increase in the intensity of symmetric vibrations of P-O-P bond, which was confirmed by the improvement of water durability with the increasing amount of Na₂O in the range of 0–10 wt.%. Substitution of 10 wt.% Na₂O led to the weight loss of the glass to 5.93 mg/cm^?2 after immersion in deionized water at 50 °C for 24 h. The results of XRD showed that the ability of crystallization decreased, indicating the good thermal stability of the glass. The glass containing 8 wt.% Na₂O had the best properties in every respect and might be an alternative to lead based glasses for the applications, providing further composition improvement.     

Non-isothermal kinetic studies for binary TeO2-P2O5 glass system

A study of TeO₂–P₂O₅ glass system has been carried out by Differential Thermal Analysis (DTA) to elucidate the kinetics of crystallization for these glassy samples. The results of DTA performed at different heating rates are discussed. The values of the glass transition temperature, T _g , as well as the glass crystallization temperature, T _c , are found to be dependent upon the heating rate. From this dependence, the values of activation energy for both the glass transition and crystallization are evaluated and discussed     

Infrared absorption spectra of evaporated V2O5 and co-evaporated V2O5/B2O3 thin films

The Fourier transform infrared spectra of different compositions of evaporated V₂O₅/B₂O₃ thin films have been investigated. Most of the absorption bands corresponding to V₂O₅ and B₂O₃ films coincide with those reported by other authors. The short-range order in amorphous V₂O₅ films is found to be conserved. The absorption spectra indicate a boroxol ring structure for B₂O₃ films. In co-evaporated V₂O₅/B₂O₃ films the boron is observed to substitute in the V₂O₅ network such that the coordination number of vanadium ion remains unchanged. The presence of a number of bands corresponding to -OH groups indicates the hygroscopic character of the films.     

Effects of glass composition on compressive strength of bioactive cement based on CaO-SiO2-P2O5 glass powders

Mixtures of CaO-SiO₂-P₂O₅-CaF₂ glass powders with 3.7 m ammonium phosphate solution give bioactive cements which can set in a few minutes and bond to living bone in a few weeks. In the present study, the mechanical strengths of the mixtures, which were held in 100% humidity at 37°C for 1 h and then soaked in a simulated body fluid (SBF) for 23 h, were investigated in terms of the glass composition. Their compressive strengths varied significantly with small changes in the CaO/SiO₂/P₂O₅ ratios under a constant CaF₂ content. Addition of CaF₂ to a CaO-SiO₂-P₂O₅ composition increased the compressive strength, whereas addition of MgO decreased it. The glass composition of CaO 47.1, SiO₂ 35.8, P₂O₅ 17.1, CaF₂ 0.75 wt ratio gave the highest compressive strength among the compositions examined: 56 and 80 MPa, respectively, after soaking in the simulated body fluid for 23 h and 3 days. The variation of the compressive strength with the glass composition was well interpreted in terms of the amount of the hydroxyapatite formed at the intergranular spaces of the glass powders in the simulated body fluid.     

Structural studies of some V2O5-P2O5-B2O3-Fe2O3 glass systems

X-ray diffraction and infrared measurements were performed on vanadium borophosphate glass containing different amounts of iron ranging from 0–7.5 mol % and heat treated at 300 °C for various times. The structure and phase separation could be determined for each glass composition. V₂O₅ was the main precipitated phase in all heat-treated samples, and its amount was dependent on the heat-treatment time and Fe₂O₃ content. Also FeP was detected in samples heat treated for 24 h. The infrared measurements showed the presence of both V⁴⁺ and V⁵⁺. The symmetry of V₂O ₇ ⁴⁻ and VO ₄ ³⁻ groups was found to increase with increasing Fe₂O₃ content. It was also found that some PO₄ changed to BO₃, forming a non-bridging oxygen.     

Optical and esr spectra of titanium (III) in Na2O-B2O3 and Na2O-P2O5 glasses

The optical absorption and the esr spectra of titanium(III) in binary Na₂O-B₂O₃ and Na₂O-P₂O₅ glasses have been studied. Titanium(III) produces two optical absorption bands around 20 000 and 14 000 cm^–1 which are assigned to the²B_2g ²B_1g and²B_2g ²A_1g transitions respectively of Ti³⁺ in a tetragonally distorted octahedral environment. The absorption bands in phosphate glasses are narrower and absorption coefficients higher than those in borate glasses. The esr spectrum of titanium(III) in all the glasses consists of a broad asymmetric line withg 1.94 in borate glasses, andg 1.92 in phosphate glasses; no hyperfine structure has been observed.     

Optical absorption spectra of evaporated V2O5 and co-evaporated V2O5/B2O3 thin films

The optical absorption spectra of evaporated V₂O₅ and co-evaporated V₂O₅/B₂O₃ thin films have been studied. For higher photon energies, the absorption is found to be due to a direct forbidden electronic transition process from the oxygen 2p band to the vanadium 3d band in a similar way to that observed in crystalline V₂O₅. The exponential behaviour of absorption edge for lower photon energies is attributed to the electronic transitions between the tailed-off d-d states corresponding to V⁴⁺ ions. For co-evaporated V₂O₅/B₂O₃ films the optical energy gap is observed to increase with the increase in V₂O₅ content of the composite films.     

Novels patterns of hydration and new compounds in the ternary system of CaO-Al2O3-P2O5

 The patterns of hydrating and solidifying with the compositional variation of phosphorus-rich, phosphorus-calcium-rich and aluminum-calcium rich regions in ternary system CaO-Al₂O₃-P₂O₅ has been studied in detail, and two new ternary compounds L and H have been synthesized here. The results indicate that the region of 48–56% P₂O₅ doesn’t present cementitiousness, which contains mainly crystal phases of β-C₂P(2CaO·P₂O₅), α-C₃P(3CaO·P₂O₅) and AlPO₄; the phosphorus-calcium-rich region of 21–35% P₂O₅ exhibits substantial cementitiousness, which contains mainly crystal phase of α-C₃P and certain amount of CA(CaO·Al₂O₃) and new phases L/H; and the aluminum-calcium-rich region of 8–18% P₂O₅ is full of promise for cementitiousness. It contains mainly new crystal phase L and certain amount of α-C₃P and CA. The hydration and solidification mechanisms have been preliminarily analyzed by means of XRD, XPS and DTA. It appears that crystal phase CA might hydrate directly to the stable phase of C₃A·6H₂O in the phosphorus-rich case of 21–35% P₂O₅; new phase H has the behavior of rapid setting; and L, being a dominant phase, can prevent cement pastes from significant strength loss in long curing cycles. Received: 12 March 1998 / Accepted: 29 July 1998     

Electrical properties and infrared spectra of TeO2-Fe2O3 glasses

The d.c. and a.c. electrical properties on TeO₂-Fe₂O₃ glasses with various compositions of PbO, B₂O₃ and SiO₂ were studied over a frequency range of 10²–10⁵ Hz and in the temperature range 300–500 K. The a.c. conductivity is proportional tow ⁿ, and the conduction mechanism is due to an electronic hopping process. The effects of composition and temperature on the dielectric constant and loss factor (tan ) were studied. The infrared absorption spectra of these glasses reveal that the addition of PbO, B₂O₃ and SiO₂ of these glasses does not introduce any new absorption band in the infrared spectrum of TeO₂-Fe₂O₃ glasses. These results prove the distribution of TeO₄ polyhedra which determines the network and basic oscillation of the building units in the tellurite glasses.     

The crystallisation of glasses from the ternary CaF2-CaAl2Si2O8-P2O5 system

A study of glasses from the ternary system CaF₂-CaAl₂Si₂O₈-P₂O₅ has been carried out. It has been shown that glasses with low phosphorus contents and high fluorite contents crystallise to fluorite. Fluorine reduces the glass transition temperature and is also required for the formation of fluorapatite (FAP). In the absence of fluorine in the glass no apatite phase is formed. Bulk nucleation of FAP is favoured for glasses with Ca:P ratios close to the apatite stoichiometry of 1.67 and with low crosslink densities. Thermal gravimetric analysis showed significant weight losses attributable to the formation of volatile silicon tetrafluoride to occur on crystallisation of the aluminium containing phases, anorthite and mullite, which supports the view that silicon tetrafluoride formation is hindered by fluorine bonding to the aluminium atoms of the glass network. Anorthite crystallisation always occurred by a surface nucleation mechanism and appeared to be favoured by the higher silicon to aluminium ratio in these glasses compared to previously studied glass compositions.